Azo compounds and material colored therewith



Patente dFeb. 29, '1944 UNITED STATES PATENT OFFICE AZO COMPOUNDS AND MATERIAL COLORED THEREWITH (James G. McNally and Joseph B. Dickey, Roches- "ter, N. Y.,.'assignors to Eastman Kodak Company, Rochester, .N. Y., a corporation of New Jersey "No Drawing. ApplicationJuly 21, 1 941, Serial No. 403,360

, 12 Claims. This invention "relates to new azo'compounds 'and"their'application to the "art 'of dyeing or coloring. Textilemateri'a'ls such as organic derivative's of cellul'os'e,"vvool,"-silk, Nylon andVinyon and lacquers composed'ofcellulose esters, cellulose ethers and vinyl derivatives, for example, can" be colored. Coloration "can be eifected by dyeing,

printing; s'tencilling orothersuitable methods.

" Typical organic derivatives of cellulose include -the hydrolyzed aswell as the -unhydrolyzed cellulose-organic acid esters suc'hascellulose acetate,

*cellulose for-mate, cellulose propionate, or cellulose "butyr'ate -andthe hydrolyzed-as well as the unhy- "dro'lyzed mixed organic acid esters of cellulose such as cellulose acetate'propionate, cellulose acetate butyra'te, an'd the cellulose ethers such'as 'methyl'cellulose, ethyl cellulose,- or benzyl cellulose.

It is an object ofour invention to provide a new class of azo compounds. provide a'processfor the'dyein'g 'or' coloration of various textile materials including organic derivatives of cellulose, Wool, silk, Nylon and Vinyon textile materials. 'A" further object is to provide dyed textilematerials which-are of; good fastness to "light and washing and which i possess ,good v resistance to burntgas fumes.

Other objects will -hereinafter appear.

The azo'compo'unds of'our invention, by means of "which the above objects are accomplished or made possible, consist of the azo compounds having the formulas:

-R-N=NR1 and ivhereinlt represents the residue of a' benzene nucleus containing a 'NOz group in para position to the azo bond' shown, Rrrepresents theresidue of a 'lalkyl-tetrahydroquinoline nucleus containing-a lo'w 'carbon alkyl=group attached to the carbon atom in its 2=position and R2 represents the residue of amember s'elected" from "the group consisting of" a l-alkyl phenmorpholme nucleus anda' 1-alkyl tetrahydroquinoline nucleus, said 1-alkyl-tetrahydroquinoline and said l-alk'ylphenmorpholine nuclei being bond -through the carbon atom in the 6-position. -While-our invention relates broadly to the azo compounds-having the: above formulas, it relates moref particularly to the 1 azo compounds having v theiormul-as:

Another object is to joined to the azo;

I v-hydroxypropyl,

advantageous and 0f.

hydroxyalkyl Nms Nigu tm and : hydroxyalkyl wherein X represents a member selected from the group consisting of hydrogen and a low carbon .a'lky] ,groupfxi represents a low carbon ,alkyl group, Q represents a member selected from the group consisting of O and CH2, Y represents a'member selected from the groupconsisting of hydrogen and a halogen atom, vY1 represents a member selected from the group consisting of hydrogen and a nitro group, Z represents a member selected from the groupconsisting cfan-alkyl group, an alkoxy group and a halogen atom and n represents a member selected from .the group consisting of 0, 1," 2andl 3.

For; purposes of clarity, it is here noted that the alkyl group attached tonthetnitrogen atom forming a, part of the tetrahydroquinoline. and phenmorpholine nucleus is ordinarily analkylgroup such as methyl, ethyl, ethyl,

= mostadvantageous. .Similarly, the presence of a amethyl; group in the 7-position-appearsto be advantageous.

-Simi'larly,;in -the interest of; clarity, it is here rgsumnotedlthattm tetrahydroquinoline and .phen or..

pholine nuclei are numbered as indicated hereinafter.

Phenmorpholine The aZo compounds of our invention constitute valuable dyes for the coloration of the materials hereinbefore named, especially for the coloration of cellulose acetate and Nylon. For the coloration of organic derivative of cellulose textile materials nuclear non-sulfonated compounds should be employed and it is to such compounds that our invention is more particularly directed. These compounds likewise can be used to color the other materials named herein. Nuclear sulfonated compounds of the invention, which can be prepared by sulfonation of the unsulfonated compounds, possess little or no utility for the coloration of organic derivative of cellulose textile materials hflt can be used to color wool and silk.

Generally speaking the dye compounds of our invention possess exceptional light fastness properties and as they yield valuable rubine and violet shades on cellulose acetate silk, one is able to dye this material light fast violet shades. So far as we are aware, revious attempts to secure such light fast violet shades on cellulose acetate have not been very successful. Our investigations lead us to believe that it is the presence of a single low carbon alkyl group, especially methyl, in the 2-position of the phenmorpholine or tetrahydroquinoline nucleus which effects such an improvement in the light fastness of the dyeings obtained. This discovery could not have been predicted.

Compounds of our invention, wherein diazotized p-nitro-o-fluoroaniline is employed have been found to yield shades which are quite dif ferent (being pinker) than those obtained where diazotized p-nitro-o-(Cl, Br, I) aniline is used. This also could not have been predicted. The new azo compounds of our invention possess the further advantages of being easily dischargeable and of having superior resistance to burnt gas fumes. Other advantages include good affinity for cellulose acetate silk and'the ability to dye this material rapidly at relatively low temperatures.

The azo compounds of our invention can be prepared by diazotizing p-m'troa-niline compounds and coupling the diazonium compounds obtained with the tetrahydroquinoline and phenmorpholine compounds indicated hereinbefore.

The following examples illustrate the preparation of the azo compounds of our invention:

EXAMPLE 1 I 1 gram mole of p-nitroaniline is cliazotized in known fashion, freed of nitrous acid by means of urea, following which the diazonium compound pling reaction which takes place is completed by aaaac'rs EXAMPLE 2 1 gram mole of l-amino-2-chloro-4-nitrobenacne is diazotized in a hydrochloric acid or sulfuric acid medium in known fashion and the diazonium compound obtained is coupled with 1 gram mole of 1pn -dihydroxypropyl-l'l-dimethyltetrahydroquinoline. Coupling and recovery of the dye compound formed can be carried out as described in Example 1. It is here noted that in preparing 7-alkyl-2-alkyltetrahydroquinolines some of the 5-alkyl-2-alkyltetrahydroquinoline compound is formed. Accordingly, it will be understood that some hon-dihydroxypropyl- 2,5-dimethyltetrahydroquinoline is present in the coupling component of this example. The dye mixture obtained colors the textile materials previously named and especially cellulose acetate silk and Nylon rubine shades which are very fast to light.

EXAMPLE 3 1 gram mole of 1-amino-ZA-dinitrobenzene is diazotized in nitrosyl sulfuric acid, freed of nitrous acid by means of urea or sulfamic acid, and the diazonium compound formed is poured into water and coupled with 1 gram mole of 1 s dihydroxypropyl 2,7 dimethyltetrahydroquinoline. Coupling and recovery of the dye compound formed can be carried out in accordance with the procedure described in Example 1. The dye compound obtained colors the textile materials named herein violet shades which are fast to light. EXAMPLE 4 1 gram mole of 1-amino-2,4-dinitro-6-chlorobenzene is diazotized in a hydrochloric acid or sulfuric acid medium and the diazom'um compound obtained is coupled with 1 gram mole of 1 fin dihydroxypropyl 2,7 dimethyltetrahydroquinoline. Coupling and recovery of the dye compound formed can be carried out in accordance with the procedure described in Example 3. The dye compound obtained colors cellulose acetate silk reddish-blue shades of excellent light fastness.

1 gram mole of 1-13-methyl-fl,v-dihydroxypropyl-2,7-dimethyltetrahydroquinoline can be substituted for the coupling component of the example to obtain a dye which similarly colors cellulose acetate silk reddish-blue shades of excellent light fastness.

EXAMPLE 5 1 gram mole of 1-amino-2,4-dinitro-6-cyanobenzene is diazotized and the diazonium compound obtained is coupled with 1 gram mole of l [3 7 dihydroxypropyl 2 ethyl 3 methyll-methoxytetrahydroquinoline. Coupling and recovery of the dye compound formed can be carried out in accordance with the generalprocedure described in Example 3. The dye compound obtained colors cellulose ester fabrics reddishblue shades fast to light.

EXAMPLE 6 1 gram mole of 1-amino-2-fluoro 4-nitrobenzene is diazotized with sodium nitrite in a hydrochloric acid or sulfuric acid medium and the diazonium compound obtained is added to an iced hydrochloric acid solution of LBJ-dihydroxypro- 1-amino-2,4-dinitro-6-iodobenzene i pyl-2,7-dirnethyltetrahydroquinoline. Th e coupling reaction which takes place is completed by adding sodium carbonate until the mixture is neutral to Congo red paper. The dye compound 3 ance with the procedure described'in Exalnple 7.

The dye compound. Obtained colorscellulose acetate silk pinkish-whine shades which are fast to 1' ht. EXAMPLE 9 l-ammo-2,4-dinitro-G-chlorobenzone 1-ami11o-2,4-dinitro-6-bromobenzene Lamina-2,4-dinitro-(i-hydroxybenzene l-amino-LA-dinitro-o-eyanobenzeue 1-amino-2- [luoroA-nitrobehzone 1 D l 1 -fi-hydroxyethyltetrahydroquinoline -ll-hydroxypropyl-2-methylphenmorpholinc -fl-hydroxypropylphenmorplioline l49-11ydroxypropyl-2-methyltetrah l-y-hydroxypropyl-2-methyltetra l-fi,'y-dihydroxypropyl-2-methyl 1-;9,-y-dihydroxypropyl-7-methyl 1-;3,'y-dihydroxypropylq-methyl formed is recovered by filtration, washed with water and dried. The dye compound thus ob 1 g am l of l m nq-?fiuq o r trqb tained colors cellulose acetate silk pinkish-violet Z9119 1S z t h dlazomumrcompqund shades which are very fast to light. obtained is coupled w1th 1 gram mole O -B-hY- E 7 droxyethyl 2-methyl-te trahydroquinoline. Coue I pling and recovery of the dye compound formed 1 gram mole of 1-amino-2 fluoro-4-nitrobencan be carried out in accordance with theprozene is diazotized and the diazonium compound ccdure described in Example 6. The dye coinobtained is added to an, acetic acid soluti n pound obtained colors cellulose acetate silk'pinkof j 1 'y sulfatopropyl 2 methylphenmorpholine. i h-I'llbinefl'hecoupling reaction Whichtakes place is comy t e Substltlltloll 0f 1 gram mole of 4 pleted by adding sodium carbonate until the d Y t y et y p e o pholine for the reaction mixture is just neutral toCorigo r'e'd' pacoupli g component of the p l' y Wmper following which th reactio mixtu 1 pound is obtained which colors cellulose acetate poured into water and the dye compound'precipi- $11k pinkiSh-Illbinev I K r ted by th additi n of di m chlo id Upon The following tabulation further illustratesthe recovery of the dye compound by filtration and compounds included within the scope of our indrying, a dye compound is obtained which colors vention together with the color they produce on cellulose acetate silk a pinkish rubine shade'which 0911111056 e te. silk- T e p n s in icated i fast to light, below may be prepared'by diazotizing the amines EXAMPLE 8 I L I i I listed undei the heading Amine and coupling 1 gram mole of 1-amino-2-fluoro-4-nitrobenthe diazonium compounds obtained Withthe comzene is diazotized and the diazonium compound pounds specified in the column entitled Couobtained is coupled with 1 gram mole of 1-sodipling component. The diazotization and couum-c-sulfoethyl-2-methyl-7-chlorotetrahydropling reactions ma for example, be carried out quinoline. Coupling and recovery of the dye following the general procedure described in Excorripound formed can be carried outin accordamples 1 to 9, inclusive.

Amine Coupling component Color p-Nitroaniline H (1) l-B,'y-dihydroxypropyla-methyltetrahydroquinolinel Rod to rubinc.

Do (2) 1-6,'y-dihydroxypropyl-2-ethyltetrahydroquinoline. I Do.- (3) 1 -B,'y-dihy dr0xypropyl-2-w-n1ethoxymethyltetrahydro quiuohne Do. (4) 1-5,y-dihydroxypropyl-Z-w-methoxyethyltetrahydroquinoline Do. (5) 1-5,'y-dihydroxypropyl-Z-propy]tetrahydroquinoline Do. (6) 1-fl-methyl fi,'y-dihydroxypropyl-2-methyltctrahydroquinoline i V l Do. (7) l-pentaerythrityl-2-methyltetrahydroquinoline Do. (8) 1-g1ycosyl-Z-methyltetrahydroquinoline Do. (9) l-B-hydroxyethyl-2-mcthyltetrahydroquinoline- Do. (10) 1-B-hydroxypropyl-Z-methyltetrahydroquinoline .7 Do. (11) l-Byy-dihydroxypropyl-2,7-dimethy1tetrahydroquinoline..l .i Do. (12) 1,-13, -dihydr0xypropyl-2,5-dimethyltetrahydroquinoli11c D0. ,(13) 1-5,'y-dihydroxypropyl-2-ethyl-5-methyltetrahydroquinoline .i A .Do. (14) 1-13,y-(1ihydroxypropyl-2-methyl-5ethyltetraoydroquinolinel Do. (15) l-fi,y-dihy iroxypropyl-2-methyl-fi-methoxytetrahydroquinoline i Do. (16) 1-;53,'y-dihydroxypropyl-2-mcthyl-7-ethoxytetrahydroquinoline.cv H M e. c A Do. (17) 1- 8, -dihydroxypropyl-2-methy1-5-methyl-8-methoxytetrahydroquinoline..H Do. (l8) l-fi diliydrpxypropyl-2-methyl-5-mcthyl-8-cthoxytotrahydroquinolino c c Do. (19) l-B, -dihydroxypropyl-2-methyl-8-methoxytetrahydroquinolinc. i. Do. (20) 1-fl,methyl-fl;y-dihydroxypropyl-2,T-(limethyltetrahydroquinoline Do. (21) l-fl-hydroxyethyl-Z,5 dimethyltetrahydroquinoline Do. Do (22) l-B, -dihydroxypropyl-2-B-hydroxyethyltetrahydroquinolino D0. l-amino-2-chloro-4-nitt0benzeno 1-22 above A. Rubne to bluishc 111 1H6 1-amino-2-bromo-4-nitrobenzene Do. l-amino-2-iodo-4-nitrobenzene I Do. 1-amino-2-eyano-4-nitrobenzene Do. l-amino-2-carbethoxy-4-nitrobenzene Do. 1-amino-2-hydroxy-4-nitrobenzene Pinkish-rubine.

l-amino-Z-(methoxy, ethoxy)-4-nitro- Rubinc.

Rubine to violet. Vigllot to reddisho. Reddish-blue to 112. Violet to reddishb u Pinkish-rubiuc.

D0. ydroquinoline c D0 hydroquinolinc Do.

tetrahydroquinolino tetrahydroquinolinc Do. Pinkish-violet phenmorpholine Do.

1-8,'wdihydroxypropyl-2,7-dimethylphenmorpholino Do. l-fi,y-dihydroXypropyl-7-ch1orophonmorpholine Plnkish-red.

3) 1-8,'y-dlhydroXypropy1-7-chl0r0tetrahydroquin0line Do.

1- 3,'y-dihydroxypropyl-5-methylphenmorpholinefln Pinkish-violot. ','y-dihydroxypropyl-l5-dimethylphenmorpholine Do. 1-5,'y-d1'hydroxypropy1-2,5-dimethyltetrahydroquinolino Do. l-pentaerythrit'yl-2-methyltetrahydroquinoline Pinkish-rubine. 1-pentaerythrityl-2,7-dimethyltetrahydroquinoliua Pinkish-violet.

9) l-pentaerythrityl-2,7-dimethylphenmorpholiue I Do.

l-B-sulfoethyl-Z-methylphenmorpholine. Pinkishkrubino. 1-{3 sulfoethyl:2J dimethylphenmorpholine Pinkisheviolet. 1-B-sulfoethyl-7-ch1oro-2-methylphenmorpholine Pinkish-red l-fl-meth0xyethyl-2-methyltetrahydroquinoline- Pinkish-rubine.

l-fi-methoxyethyl-Z-methylphenmorpholine Do.

The tetrahydroquinoline coupling compounds employed in the preparation of the azo compounds of our invention can be prepared by hydrogenating the corresponding quinoline compounds, unsubstituted. in the ring nitrogen atom, and then introducing the alkyl substituent present on the ring nitrogen atom by methods known to the art for their introduction. The examples given hereinafter are illustrative of the hydrogenation and alkylation reactions employed.

HYDROGENATION Preparation of Z-methyl tetrahydroquirtoline One gram mole of Z-methyl quinoline is reacted with hydrogen at a temperature of about 90 C. in the presence of grams of a finely divided nickel catalyst such as Raney nickel under a hydrogen pressure of about 1500 pounds per square inch. Upon completion of the reaction, the 2- methyl tetrahydroquinoline formed is recovered, for example, by distillation under reduced pressure. Completion of the reaction can be determined, for example, by measuring the amount of hydrogen added to the pressure vessel to obtain the desired pressure and then, while maintaining the desired pressure, adding hydrogen until the amount required to produce the tetrahydroquinoline compound has been introduced. Again if excess hydrogen is originally added to the pressure vessel and no further hydrogen added the reaction is complete when the pressure remains substantially constant. As will be understood, the temperature and pressure conditions employed can be varied over wide limits. Those given, however, are suitable and can be used to successfully hydrogenate other quinoline compounds to obtain the corresponding tetrahydroquinoline compounds.

ALKYLATION Preparation of 1-/3,' -dihydro:rypropyl-2- methyl tetrahydroquinoline 1 gram mole of Z-methyl tetrahydroquinoline, 1.2 gram mole of sodium bicarbonate and 1.2 gram mole of glyceryl chlorohydrin are heated together in a reaction vessel with stirring at 140 C. for five hours. Following completion of the reaction, water is added to the reaction mixture which is then steam distilled to remove any unreacted 2-methyl tetrahydroquinoline. The desired compound is then recovered from the reaction mixture in known fashion and can be used without further purification.

Preparation of 1 -s-hydrorcyethyZ-2J-dimethyl tetrahydroquino-Zine 1 gram mole of 2,7-dimethyl tetrahydroquinoline is charged into an autoclave and heated at 180 C. with 1.1 gram mole of ethylene oxide for six hours. The reaction mixture is then permitted to 0001 following which the desired product-is recovered by distilling the reaction mixture under reduced pressure.

Preparation of 1-sodium-p-sulfoethyl-7-chlorotetrahydroquinoline 1 gram mole of '7-chlorotetrahydroquinoline, 1.1 gram mole of Sodium-fi-bromoethanesulfonate and 1.1 gram mole of sodium bicarbonate are heated together in a suitable reaction vessel to -150 C. for several hours. When nomore carbon dioxide is evolved, the reaction mixture is poured into water, steam distilled to remove unreacted 7-chlorotetrahydroquinoline and the remaining solution concentrated to produce crystallization of the desired product.

The phenmorpholine coupling compounds employed in the preparation of the azo compounds of our invention can be prepared by alkylation of the corresponding phenmorpholine compounds which are unsubstituted in the ring nitrogen atom. Alkylation can be carried out in the same manner as described for the tetrahydroquinoline compounds and is illustrated by the following examples.

Preparation of 1-' -hydr0a:ypropyl-Z-methyl phenmorpholine 1 gram mole of Z-methyl phenmorpholine is reacted with 1.1 gram mole of trimethylene chlorohydrin and. 0.6 gram mole of sodium carbonate in a suitable reaction vessel at C. for five hours. The desired product may be recovered from the reaction mixture by distillation under reduced pressure.

Preparation of 1-sodium-c-suljatoethyl-2,7-

clz'methyl phenmorpholine 1 gram mole of l-fi-hydroxyethyl-Zfl-dimethylphenmorpholine are dissolved in carbon tetrachloride and 1 gram mole of chlorosulionic acid is added and the reaction conducted without heating; the reaction being completed by warming slightly. Sodium carbonate is then added to the reaction mixture until it is neutral to Congo red paper. The carbon tetrachloride may be largely removed by distillation following which the desired product can be obtained by crystallization on evaporation of the remaining carbon tetrachloride.

Additional information regarding the preparation of phenmorpholine compounds is to be found in McNally and Dickey U. S. Patent No. 2,196,222, issued April 9, 1940. Similarly, additional information concerning the preparation of tetrahydroquinoline compounds will be found in Dickey and McNally application Serial No. 306,201, filed November 25, 1939.

The azo compounds of our invention are, for the most part, relatively insoluble in water and, accordingly, they may be advantageously directly applied to the material undergoing coloration in the form of an aqueous suspension which can be prepared by grinding the dye to a paste in the presence of a sulfonated oil, soap or other suitable dispersing agent and dispersing the resulting paste in water. In some instances, the dye may possess sufficient solubility in water as to render the use of a dispersing agent unnecessary. Generally speaking, however, the use of a dispersing agent is desirable.

Direct dyeing operations can, with advantage, be conducted at temperatures of about 75-85 C.

but any suitable temperature may be used. Thus, the textile material to be'dye'do'r colored is o'rdi narily added to the dyebathat a" temperature lower 'than'that at whichthemain portionof the dyeing" is to be effected, a'temperature approximating 45-55? C, for example; following which the temperature is raised-to that selected for carrying out th'e'dyeing'operation. "'I'he't'ernpera ture at which the dyeing is conductdniay; of course, be varied "somewhat depending upon the particular material undergoing colorationr- As is understood by those skilled in the art,"the in"- tensity of dyeing can'be varied by varying the proportion of dye to material undergoing coloration. Generally speaking, 1-3% by weight of dye to material is employed although any desired proportions can be -used.-

Suitable dispersing agents together with the amounts that may be employed are disclosed in McNally and Dickey Patent No. 2,115,030, issued April 26, 1938. The process disclosed in this pat ent'for the dyeing of 'cellulose' acetate silk can beused in applying the dyes of the present application to this material.

' It will be understood that the other textile materials named hereinbefore can be directly colored from an aqueous dyebath in a similar manner as Cellulose acetate silk; However, other suitable methods for the dyeing of these materials are known to those skilled in the art and these methods, of course, can be used in'applying the dye compounds of this application if desired. We would further note that, while colors yielded by the dye compounds have been given primarily with reference to cellulose acetate silk, generally similar colors are ordinarily obtained on the other materials.

We claim:

1. The azo compounds having the formula:

wherein R2 represents the residue of a l-alkyl tetrahydroquinoline nucleus containing a low carbon alkyl hydrocarbon group attached to the carbon atom in its 2-position and wherein said l-alkyl tetrahydroquinoline nucleus is joined to the azo bond shown through the carbon atom in its 6-position.

2. The azo compounds having the formula:

wherein R. represents the residue of a benzene nucleus containing a N02 group in para position to the azo bond shown, R1 represents the residue of a l-alkyl tetrahydroquinoline nucleus containing a low carbon alkyl hydrocarbon group attached to the carbon atom in its 2-position and wherein said l-alkyl tetrahydroquinoline nucleus is joined to the azo bond shown through the carbon atom in its fi-position.

3. The azo compounds having the formula:

wherein X1 represents a low carbon alkyl hydrocarbon group, Y represents a member selected from the group consisting of hydrogen and a halogen atom, Y1 represents a member selected from the group consisting of hydrogen and a nitro= group', Z represents a member selected -from the groupconsi'sting-of an alkyl group, an alkoxy group and-a halogen atom and n'represents a member" selected from the group consisting of 0; 1, 2 and '3. r 1

4. The azo compounds having the formula:

Y1 wherein R3 represents a fi,'ydihydroxypropyl radical. Y represents a member selected from the group consisting of hydrogen and a halogen atom and Y1 represents a member'selectedfrom the grbupconsisting' of hydrogen anda nitro group. -5.-The azo compound-havingthe formula:

wherein R represents the residue of a benzene nucleus containing a nitro group in para position to the azo bond shown, B represents the residue of a benzene nucleus, X1 represents a low carbon alkyl hydrocarbon group, wherein the nitrogen atom numbered 1 is joined to a carbon atom of the benzene nucleus B in para DOSitiOH azo bond shown and wherein the carbon atom numbered 4 is joined to a carbon atom or the benzene nucleus B in meta position to the azo bond shown and wherein the tetrahydroquinoiine nucleus is joined to the azo bond shown through the carbon atom in its 6-position.

8. The azo compound having the formula:

omononornou o-orn 9. Textile material colored with an azo dye compound having the formula:

RN=NR1 wherein R represents the residue of a benzene nucleus containing a nitro group in para position to the azo bond shown, R1 represents the residue of a l-alkyltetrahydroquinoline nucleus containing a low carbon alkyl hydrocarbon group attached to the carbon atom in its 2-position and wherein said 1-alkyltetrahydroquinoline nucleus hydroxyalkyl H9 wherein R represents the residue of a benzene nucleus containing a nitro group in para position to the azo bond shown, B represents the residue of a benzene nucleus, X1 represents a low carbon alkyl hydrocarbon group, wherein the nitrogen atom numbered 1 is joined to a carbon atom of the benzene nucleus B in para position to the azo bond shown'and wherein the carbon atom numbered 4 is joined to a carbon atom of the benzene nucleus B in meta position to the azo bond shown and wherein the tetrahydroquinoline nucleus is joined to the azo bond shown through the carbon atom in its 6-position.

11. A cellulose acetate colored with a nuclear non-sulfonated azo dye compound having the formula:

wherein R represents the residue of a benzene nucleus containing a nitro group in para position to the azo bond shown, R1 represents the residue of a l-alkyltetrahydroquinoline nucleus containing a low carbon alkyl hydrocarbon group attached to the carbon atom in its 2-position and wherein said l-alkyltetrahydroquinoline nucleus is joined to the azo bond shown through the carbon atom in its 6-position.

12. A cellulose acetate colored with a nuclear non-sulfonated azo dye compound having the formula:

wherein R. represents the residue of a benzene nucleus containing a nitro group in para position to the azo bond shown, B represents the residue of a benzene nucleus, X1 represents a low carbon atom alkyl hydrocarbon group, wherein the nitrogen atom numbered 1 is joined to a carbon atom of the benzene nucleus B in para position to the azo bond shown and wherein the carbon atom numbered 4 is joined to a carbon atom of the benzene nucleus B in meta position to the azo bond shown and wherein the tetrahydroquinoline nucleus is joined to the azo bond shown through the carbon atom in its fi-position.

JAMES G. MCNALLY. JOSEPH B. DICKEY. 

